U.S. patent application number 13/505277 was filed with the patent office on 2012-11-01 for hybrid-type polyester resin, resin composition for formation of film, and polyester film and textile.
Invention is credited to Koji Maeda, Yusuke Numamoto.
Application Number | 20120277381 13/505277 |
Document ID | / |
Family ID | 43922099 |
Filed Date | 2012-11-01 |
United States Patent
Application |
20120277381 |
Kind Code |
A1 |
Maeda; Koji ; et
al. |
November 1, 2012 |
HYBRID-TYPE POLYESTER RESIN, RESIN COMPOSITION FOR FORMATION OF
FILM, AND POLYESTER FILM AND TEXTILE
Abstract
Provided is a hybrid-type polyester resin which, when used in
processing a base material such as textile or PET film, can impart
excellent flame retardance to the base material. The hybrid-type
polyester resin can be inhibited from scattering high-temperature
drips, even if the hybrid-type polyester resin burns. The
hybrid-type polyester resin comprises both a polyester resin and a
siloxane prepared from silica and an alkoxysilane. Therefore, the
hybrid-type polyester resin retains the excellent properties
inherent in polyester resin and exhibits extremely excellent flame
retardance by virtue of hybridization with the siloxane. Even if
the hybrid-type polyester resin burns, the hybrid-type polyester
resin is less susceptible to deformation, and is therefore
inhibited from scattering high-temperature drips.
Inventors: |
Maeda; Koji; (Kyoto, JP)
; Numamoto; Yusuke; (Osaka, JP) |
Family ID: |
43922099 |
Appl. No.: |
13/505277 |
Filed: |
October 28, 2010 |
PCT Filed: |
October 28, 2010 |
PCT NO: |
PCT/JP2010/069158 |
371 Date: |
June 26, 2012 |
Current U.S.
Class: |
525/446 |
Current CPC
Class: |
C08G 63/6954 20130101;
D06M 2200/30 20130101; C08G 63/914 20130101; D06M 15/507 20130101;
C08G 77/04 20130101; C09D 5/18 20130101 |
Class at
Publication: |
525/446 |
International
Class: |
C08G 63/91 20060101
C08G063/91; C08G 63/78 20060101 C08G063/78 |
Foreign Application Data
Date |
Code |
Application Number |
Nov 2, 2009 |
JP |
2009-252225 |
Claims
1. A manufacture method for a hybrid-type polyester resin,
comprising a step of forming the hybrid-type polyester resin by
reacting a reaction solution by a sol-gel method: wherein the
reaction solution contains a polyester resin, silica particles and
an alkoxysilane.
2. The manufacture method for the hybrid-type polyester resin
according to claim 1, wherein the polyester resin contains an
aqueous polyester resin formed from a polyvalent carboxylic acid
component, a glycol component and a hydrophilic component.
3. The manufacture method for the hybrid-type polyester resin
according to claim 1, wherein the polyester resin contains a
phosphorus-containing polyester resin.
4. The manufacture method for the hybrid-type polyester resin
according to claim 3, wherein the phosphorus-containing polyester
resin is formed from a polyvalent carboxylic acid component, a
glycol component, a hydrophilic component and a reactive
phosphorus-containing compound.
5. The manufacture method for the hybrid-type polyester resin
according to claim 1, wherein a phosphorus flame retardant is
placed in the reaction solution.
6. A resin composition for formation of film containing the
hybrid-type polyester resin according to claim 10.
7. A polyester film, surface-treated with the resin composition for
formation of film according to claim 6.
8. A textile treated with the resin composition for formation of
film according to claim 6.
9. The manufacture method for the hybrid-type polyester resin
according to claim 1, wherein the silica in the range of 1 mass %
to 60 mass % and the alkoxysilane in the range of 0.3 mass % to 20
mass % are placed in the polyester resin, respectively.
10. A hybrid-polyester resin manufactured by the manufacture method
according to claim 1.
Description
TECHNICAL FIELD
[0001] The present invention relates to a hybrid-type polyester
resin provided with high burn resistance, to a resin composition
for formation of film containing this hybrid-type polyester resin,
and to a polyester film and textile processed with this resin
composition for formation of film.
BACKGROUND ART
[0002] Because of the superior mechanical properties and chemical
characteristics for which it is well known, polyester resin is
widely used not only for clothing and industrial and other
textiles, but also as a base material for magnetic tapes, flexible
disks and other magnetic recording materials, as a base material
for photographs, electrical insulation, cable wrapping, capacitors,
evaporation coatings, adhesive tape, printer ribbons and magnetic
cards, for mold release of FRP and the like, in packaging, and in
various agricultural and other industrial applications.
[0003] Recently, there has been increasing demand for improvements
in the burn resistance of synthetic fibers and various plastic
products from the standpoint of fire prevention, but conventional
polyester resin is unsatisfactory in terms of burn resistance.
Therefore, efforts have been made to impart flame retardancy by
adding organic halogen compounds, antimony compounds and other
flame retardants during polyester manufacture and the like.
[0004] One problem with these flame retardants is that they produce
toxic gas in contact with flame, and it has therefore been proposed
that a hydrated metal compound such as aluminum hydroxide or
magnesium hydroxide be added instead, but a large amount must be
added in order to impart sufficient flame retardancy, detracting
from the excellent properties inherent in polyester resin.
[0005] To resolve these problems, methods have been proposed
whereby specific phosphorus compounds are added or copolymerized as
flame retardants during polyester manufacture (Japanese Patent
Application Publication Nos. H6-16796, 2001-139784,
2001-163962).
[0006] However, these phosphorus-containing polyester resins have
often been hardly soluble in toluene, xylene and other widely-used
organic solvents. As a result, an extremely low degree of
polymerization has been necessary in order to obtain a solution or
dispersion of a phosphorus-containing polyester resin for
processing textiles or PET films or the like using these
widely-used organic solvents, making it difficult to maintain the
inherent properties of the polyester resin. It has thus been
necessary to use organic solvents with high solubility such as
dioxane, DMF, HFIP, OCP and the like so that such
phosphorus-containing polyester resins can be coated as base
material processing treatment resins for processing, for example,
textiles and PET films while maintaining a high degree of
polymerization and preserving the inherent properties of the
polyester resin, but although these solvents have high solubility,
they have problems in terms of working environment and
environmental protection.
[0007] To resolve these problems, the applicants in this case have
proposed including a reactive phosphorus-containing compound in the
reaction system during polyester synthesis (Japanese Patent
Application Publication No. 2004-67910). In this way, a polyester
resin can be made flame retardant while maintaining the excellent
properties inherent in polyester resin.
[0008] As thus described polyester resin has been made more flame
retardant, but the inventors have continued to make improvements in
polyester resin in order to further enhance the flame retardancy of
polyester resin for purposes of fire prevention and the like, and
to impart additional characteristics to the polyester resin for
purposes of fire prevention and the like. The inventors also
focused on the scattering of high-temperature droplets from
polyester resin after combustion when the polyester resin burns,
and conceived the idea that even when polyester resin burns, the
damage can be prevented from spreading if such scattering of
droplets can be prevented.
DISCLOSURE OF THE INVENTION
[0009] In light of these circumstances, it is an object of the
present invention to provide a hybrid-type polyester resin that can
impart excellent flame retardancy to textiles, PET films and other
base materials when used in processing these materials, and that
can suppress scattering of high-temperature droplets even when
combustion occurs, along with a resin composition for formation of
film containing this hybrid-type polyester resin, and a polyester
film and textile treated with this resin composition for formation
of film.
[0010] The hybrid-type polyester resin of the present invention
comprises a polyester resin and a siloxane formed from silica and
an alkoxysilane. This hybrid-type polyester resin retains the
excellent properties inherent in polyester resin and exhibits
extremely high flame retardancy by virtue of hybridization with the
siloxane. Even if the hybrid-type polyester resin burns, moreover,
it is less susceptible to deformation and therefore less likely to
scatter high-temperature droplets.
[0011] In the present invention, the polyester resin preferably
comprises an aqueous polyester resin formed from a polyvalent
carboxylic acid component, a glycol component and a hydrophilic
component (water-solubility imparting component). This gives the
hybrid-type polyester resin the property of dispersing or
dissolving in aqueous solvents by virtue of the hydrophilic
component (water-solubility imparting component) while retaining
the excellent properties inherent in polyester resin, which is
highly desirable from the standpoint of ensuring worker safety,
environmental protection, ease of processing the base material and
the like.
[0012] In the hybrid-type polyester resin of the present invention,
moreover, the polyester resin preferably comprises a
phosphorus-containing polyester resin. This gives the hybrid-type
polyester resin even greater flame retardancy while retaining the
excellent properties inherent in polyester resin.
[0013] Moreover, in the hybrid-type polyester resin of the present
invention the phosphorus-containing polyester resin is preferably
formed from a polyvalent carboxylic acid component, a glycol
component, a hydrophilic component and a reactive
phosphorus-containing compound. This gives the hybrid-type
polyester resin even greater flame retardancy as well as the
property of dispersing or dissolving in aqueous solvents by virtue
the hydrophilic component, while retaining the excellent properties
inherent in polyester resin.
[0014] The hybrid-type polyester resin of the present invention
preferably also contains a phosphorus-based flame retardant. This
imparts even greater flame retardancy to the hybrid-type polyester
resin.
[0015] The resin composition for formation of film of the present
invention preferably contains the aforementioned hybrid-type
polyester resin. Thus, while retaining the excellent properties
inherent in polyester resin, this resin composition for formation
of film has improved flame retardancy, is resistant to deformation
during combustion, and is less likely to scatter droplets at high
temperatures.
[0016] This resin composition for formation of film is preferably a
composition to use for surface-processing of a polyester film. The
surface of a polyester film that is surface-treated with this resin
composition for formation of film thereby acquires excellent flame
retardancy, and resistance to scattering of high-temperature
droplets during combustion.
[0017] This resin composition for formation of film is preferably a
composition for textile processing. A textile that is processed
with the resin composition for formation of film thereby acquires
excellent flame retardancy and resistance to scattering of
high-temperature droplets during combustion.
[0018] A polyester film of the present invention is preferably one
that has been surface-treated with the aforementioned resin
composition for formation of film. This polyester film thereby
acquires excellent flame retardancy and resistance to scattering of
high-temperature droplets during combustion.
[0019] A textile of the present invention is preferably one that
has been treated with the aforementioned resin composition for
formation of film. This textile thereby acquires excellent flame
retardancy and resistance to scattering of high-temperature
droplets during combustion.
BEST MODE FOR CARRYING OUT THE INVENTION
[0020] Embodiments of the present invention are explained
below.
[0021] The hybrid-type polyester resin is manufactured via a step
in which a reaction solution containing a polyester resin, silica
particles and an alkoxysilane is reacted by the sol-gel method.
[0022] The polyester resin is obtained via a step in which a
polyvalent carboxylic acid component and a glycol component as raw
materials are reacted and condensed or polycondensed.
[0023] The polyvalent carboxylic acid component consists of one or
more compounds selected from the bivalent and higher polyvalent
carboxylic acids and anhydrides, esters, acid chlorides, halides
and other derivatives of these polyvalent carboxylic acids that
react with the glycol component described below to form esters
(ester-forming derivatives of polyvalent carboxylic acids).
[0024] Examples of the polyvalent carboxylic acid include aromatic
dicarboxylic acids, aliphatic dicarboxylic acids and other
dicarboxylic acids. Examples of aromatic dicarboxylic acids include
terephthalic acid, isophthalic acid, phthalic acid, diphenic acid,
naphthalic acid, 1,2-napthalenedicarboxylic acid,
1,4-napthalenedicarboxylic acid, 1,5-napthalenedicarboxylic acid
and 2,6-napthalenedicarboxylic acid. Examples of aliphatic
dicarboxylic acids include linear, branched and cyclic oxalic acid,
malonic acid, succinic acid, maleic acid, itaconic acid, glutaric
acid, adipic acid, pimelic acid, 2,2-dimethylglutaric acid, suberic
acid, azelaic acid, sebacic acid, dodecanedioic acid,
1,3-cyclopentanedicarboxylic acid, 1,4-cyclohexanedicarboxylic
acid, diglycolic acid, thiodipropionic acid and the like.
[0025] Each of these polyvalent carboxylic acids and ester-forming
derivatives thereof may be used alone, or multiple kinds may be
used together. Of these polyvalent carboxylic acids and
ester-forming derivatives thereof, terephthalic acid, isophthalic
acid, 2,6-naphthalenedicarboxylic acid and other aromatic
dicarboxylic acids and succinic acid, adipic acid, sebacic acid,
dodecanedioic acid and other aliphatic dicarboxylic acids can be
used by preference from the standpoint of ease of the reaction and
weather resistance, durability and the like of the resulting resin.
Optimally, an aromatic dicarboxylic acid is used alone as the
polyvalent carboxylic acid component, or as the principal component
of the polyvalent carboxylic acid component.
[0026] Glycol components include not only glycols but also
diacetate compounds corresponding to glycols, and other glycol
derivatives that form esters by reacting with the polyvalent
carboxylic acid component (glycol ester-forming derivatives).
[0027] Examples of such glycols include ethylene glycol and
diethylene glycol, triethylene glycol, tetraethylene glycol,
pentaethylene glycol, hexaethylene glycol, heptaethylene glycol,
octaethylene glycol and other polyethylene glycols, propylene
glycol and dipropylene glycol, tripropylene glycol, tetrapropylene
glycol and other polypropylene glycols, and 1,3-propanediol,
1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol,
2,2-dimethyl-1,3-propanediol, 2-ethyl-2-butyl-1,3-propanediol,
2-ethyl-2-isobutyl-1,3-propanediol, 2,2,4-trimethyl-1,6-hexanediol,
1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol,
1,4-cyclohexanedimethanol, 2,2,4,4-tetramethyl-1,3-cyclobutanediol,
4,4'-dihydroxybiphenol, 4,4'-methylenediphenol,
4,4'-isopropylidenediphenol, 1,5-dihydroxynaphthaline,
2,5-dihydroxynapthaline, 2,2-bis(4-hydroxyphenyl)propane (bisphenol
A), bisphenol S and the like. Each of these glycols and
ester-forming derivatives thereof may be used alone, or multiple
kinds may be used together.
[0028] Of these glycols and ester-forming derivatives thereof,
particularly ethylene glycol, diethylene glycol, 1,4-butanediol and
other butanediols, 1,6-hexanediol and other hexanediols,
1,4-cyclohexanedimethanols, and neopentyl glycol and bisphenol A
and the like can be used by preference from the standpoint of ease
of the reaction and durability and the like of the resulting
resin.
[0029] The raw materials of the polyester resin preferably also
include a hydrophilic component (water-solubility imparting
component). The hydrophilic component reacts with the other raw
materials to constitute part of the skeletal structure of the
polyester resin, thereby introducing ionic polar groups derived
from the hydrophilic component into the skeleton of the polyester
resin and imparting hydrophilicity to the polyester resin. It is
thereby possible to make the polyester resin aqueous and capable of
being dispersed or dissolved in aqueous solvents.
[0030] A component corresponding to either the polyvalent
carboxylic acid component or glycol component may also be used as a
hydrophilic component (water-solubility imparting component).
Examples of hydrophilic components corresponding to polyvalent
carboxylic acid components include dicarboxylic acids having metal
sulfonate groups, tribasic acid anhydrides, tetrabasic acid
anhydrides and other trivalent and higher polyvalent carboxylic
acids, and ester forming derivatives of these and the like.
[0031] Of these hydrophilic components, examples of dicarboxylic
acids having metal sulfonate groups and ester-forming derivatives
thereof (hereunder generally called dicarboxylic acids having metal
sulfonate groups and the like) include 5-sulfoisophthalic acid,
2-sulfoisophthalic acid, 4-sulfoisophthalic acid, sulfoterephthalic
acid, 4-sulfonaphthalene-2,6-dicarboxylic acid and other alkali
metal salts and esters of these, and acid chlorides, halides and
other ester-forming derivatives and the like. For purposes of
imparting good water dispersibility or water solubility to the
aqueous polyester resin, the aforementioned alkali metal is
preferably sodium, potassium or lithium.
[0032] When dicarboxylic acids having metal sulfonate groups and
the like are used as hydrophilic components, the metal sulfonate
groups remain effectively in the polyester resin, imparting
superior hydrophilicity to the polyester resin. Using 5-sodium
sulfoisophthalic acid or an ester thereof (such as sodium dimethyl
5-sulfonatoisophthalate) in particular, the sodium sulfonate groups
remain effectively in the polyester resin, imparting superior
hydrophilicity to the polyester resin.
[0033] It is also desirable to use trivalent or higher polyvalent
carboxylic acids and ester forming derivatives thereof (hereunder
generally called trivalent or higher polyvalent carboxylic acids
and the like) as hydrophilic components. In this case, when the
polyester resin is prepared by a condensation or polycondensation
reaction and the reaction is terminated with carboxyl groups
derived from the trivalent or higher polyvalent carboxylic acids
and the like remaining in the resin framework, the remaining
carboxyl groups can be neutralized with a basic compound such as
ammonia, alkanolamine or an alkali metal compound to make the
polyester resin dispersible or soluble in an aqueous solvent.
[0034] Example of such trivalent or higher polyvalent carboxylic
acids and the like include hemimellitic acid, trimellitic acid,
trimesic acid, mellophanic acid, pyromellitic acid,
benzenepentacarboxylic acid, mellitic acid,
cyclopropane-1,2,3-tricarboxylic acid,
cyclopentane-1,2,3,4-tetracarboxylic acid, ethanetetracarboxylic
acid and other polyvalent carboxylic acids, and ester forming
derivatives of these. By using trimellitic anhydride, pyromellitic
anhydride and ester forming derivatives of these in particular, it
is possible to adequately control three-dimensional crosslinking of
the polyester resin and effectively retain carboxyl groups in the
polyester resin after the polycondensation reaction.
[0035] By using at least one such trivalent or higher polyvalent
carboxylic acid or the like and particularly a tribasic acid
anhydride or tetrabasic acid anhydride or an ester forming
derivative thereof as a water solubility imparting component, it is
possible to effectively retain carboxyl groups in the aqueous
polyester resin and impart excellent hydrophilicity to the
polyester resin.
[0036] One of the aforementioned trivalent or higher polyvalent
carboxylic acids and the like or dicarboxylic acids having metal
sulfonate groups and the like can be used as a hydrophilic
component, or two or more may be combined.
[0037] When using a hydrophilic component corresponding to a
polyvalent carboxylic acid component, the amount of the hydrophilic
component used is preferably in the range of 1 mol % to 60 mol % of
the total polyvalent carboxylic acid component. It is thus possible
to impart particularly good hydrophilicity to the polyester resin
while also maintaining good resin strength. If the amount used is
in the range of 2 mol % to 40 mol % in particular, it is possible
to impart especially high flame retardancy, durability and the like
to a film formed from a composition for film formation containing
the polyester resin.
[0038] When a dicarboxylic acid having a metal sulfonate group or
the like is used as a hydrophilic component, the amount of the
dicarboxylic acid having metal sulfonate groups or the like used is
preferably in the range of 1 mol % to 60 mol % of the total
polyvalent carboxylic acid component. This makes it possible to
improve the resin strength of the polyester resin in particular, to
improve the tensile breaking strength and the like, and when this
polyester resin is used to prepare a composition for film
formation, to impart especially good water resistance and
durability on a film formed from the composition for film
formation.
[0039] In particular, when one or more selected from 5-sodium
sulfoisophthalic acid and ester forming derivatives thereof is used
as a dicarboxylic acid having metal sulfonate groups, the sodium
sulfonate groups can be adequately retained in the polyester resin
and excellent water dispersibility or water solubility can be
imparted to the polyester resin if the total amount of the 5-sodium
sulfoisophthalic acid and ester forming derivatives thereof used is
in the range of 1 mol % to 60 mol % of the total polyvalent
carboxylic acid component. Particularly excellent effects are
obtained if the total amount of the 5-sodium sulfoisophthalic acid
and ester forming derivatives thereof used is in the range of 1 mol
% to 30 mol %.
[0040] When a trivalent or higher polyvalent carboxylic acid or the
like is used as a hydrophilic component, the amount of the
trivalent or higher polyvalent carboxylic acid or the like used is
preferably in the range of 1 mol % to 60 mol % of the total
polyvalent carboxylic acid component. In this case, a polyester
resin having a sufficient degree of polymerization and water
dispersibility or water solubility can be obtained when the
polyester resin is manufactured under polymerization conditions
that exclude unnecessary crosslinking reactions. When a trivalent
or higher polyvalent carboxylic acid or the like is used alone as
the hydrophilic component, the amount of the trivalent or higher
polyvalent carboxylic acid and the like used is preferably in the
range of 5 mol % to 40 mol % of the total polyvalent carboxylic
acid component.
[0041] When using a trivalent or higher polyvalent carboxylic acid
or the like selected from the tribasic salts, tetrabasic salts and
ester forming derivatives of these in particular, enough carboxyl
groups can be retained in the polyester resin and excellent water
dispersibility or water solubility can be imparted to the polyester
resin if the total amount of these tribasic acid, tetrabasic acid
and ester forming derivatives thereof used is in the range of 1 mol
% to 60 mol % of the total polyvalent carboxylic acid component.
Especially desirable results are obtained if the total amount of
these tribasic salts, tetrabasic salts and ester forming
derivatives thereof used is in the range of 1 mol % to 30 mol
%.
[0042] In this Description, a water-based solvent may be water
alone or a mixed solvent comprising water and a hydrophilic
solvent. Examples of hydrophilic solvents include methanol,
ethanol, 2-propanol and other alcohols, propylene glycol monomethyl
ether, ethyl cellosolve, butyl cellosolve and other glycol ethers,
and cyclohexanone and the like. In the aforementioned mixed solvent
comprising water and a hydrophilic solvent, the ratio of the water
and hydrophilic solvent is not particularly limited, but the
content of the hydrophilic solvent in the mixed solvent is
preferably in the range of 0.1 wt % to 50 wt % considering the
stability of the polyester resin solution, the safety of the
working environment and the like.
[0043] When a trivalent or higher polyvalent carboxylic acid or the
like is used for the hydrophilic component, the aqueous polyester
resin becomes dispersible or soluble in water-based solvents by
being neutralized with a basic compound such as ammonia or
alkanolamine for example as discussed above, but the aforementioned
still applies even when such means are used.
[0044] A reactive phosphorus-containing compound is preferably
included in the raw materials of the polyester resin. This reactive
phosphorus-containing compound reacts with the other raw materials
to constitute part of the skeletal structure of the polyester resin
and contribute phosphorus atoms to the skeleton of the polyester
resin. This improves the flame retardancy of the polyester
resin.
[0045] A compound that can react and be condensed or polycondensed
with at least one of the aforementioned polyvalent carboxylic acid
component and glycol component can be used as this reactive
phosphorus-containing compound. Specifically, the reactive
phosphorus-containing compound is preferably one having an
ester-forming functional group in the molecule.
[0046] This ester-forming functional group is a functional group
that forms an ester bond by reacting with another carboxyl group or
hydroxyl group, and in addition to carboxyl and hydroxyl groups,
examples include groups derived from carboxyl groups by
anhydridization, esterification, acid chloride formation,
halogenation or the like that form ester bonds by reacting with
other hydroxyl groups (ester-forming derivative groups of carboxyl
groups), and groups derived from hydroxyl groups by acetate
formation or the like that form ester bonds by reacting with other
carboxyl groups (ester-forming derivative groups of hydroxyl
groups). An ester-forming functional group that is a carboxyl or
hydroxyl group is particularly desirable for obtaining good
reactivity in the manufacturing step.
[0047] It is especially desirable for the reactive
phosphorus-containing compound to have one or two ester-forming
functional groups per molecule. In this case, an aqueous polyester
resin having a sufficient degree of polymerization can be obtained
when the aqueous polyester resin is manufactured under
polymerization conditions that exclude unnecessary crosslinking
reactions. When the reactive phosphorus-containing compound has two
ester-forming functional groups, moreover, better effects are
obtained if both the ester-forming functional groups are carboxyl
groups, or if both the ester-forming functional groups are hydroxyl
groups.
[0048] From the standpoint of ease of the reaction and particularly
good flame retardant effects and the like, the compounds
represented by General Formulae (I) to (III) below are desirable
examples of the aforementioned reactive phosphorus-containing
compound. Of these, particularly good weather resistance of the
polyester resin and stability and the like of a resin composition
for film formation prepared from this polyester resin are obtained
using the compound represented by General Formula (I).
##STR00001##
[0049] (In the formula, R.sup.1 to R.sup.8 may be the same or
different, and each represents a hydrogen atom or organic group. A
represents a hydrogen atom or organic group, and may be the same as
R.sup.1 to R.sup.8 or different. However, at least one of R.sup.1
to R.sup.8 and A has an ester-forming functional group.)
##STR00002##
[0050] (In the formula, R.sup.9 and R.sup.10 may be the same or
different, and each represents a hydrogen atom or organic group.
However, at least one of R.sup.9 and R.sup.10 has an ester-forming
functional group.)
##STR00003##
[0051] (In the formula, R.sup.11 to R.sup.13 may be the same or
different, and each represents a hydrogen atom or organic group.
However, at least one of R.sup.11 to R.sup.13 has an ester-forming
functional group.) The compounds represented by General Formulae
(I) to (III) preferably have one or two ester-forming functional
groups per molecule.
[0052] The organic groups in General Formulae (I) to (III) above
are selected from suitable substituents without any particular
limitations, but univalent organic groups with 1 to 1,000 carbon
atoms are preferred. Examples of univalent organic groups include
alkyl, alkenyl and other aliphatic hydrocarbon groups, cyclohexyl
and other alicyclic hydrocarbon groups, aryl and other aromatic
hydrocarbon groups, aralkyl and other hydrocarbon groups, and
carboxyl and alkyloxy groups and the like. These groups may also
contain functional groups within them. For example, they may have
substituents comprising ester forming functional groups (carboxyl
groups, hydroxyl groups and ester forming derivative groups derived
from these). However, as discussed above, the number of
ester-forming functional groups per molecule is preferably one or
two.
[0053] The compound represented by General Formula (I) above
preferably has one or two ester-forming functional groups, and
these ester-forming functional groups are preferably located within
the organic group A. Of the compounds represented by General
Formula (I) above, those in which R.sup.1 to R.sup.8 are hydrogen
atoms and A has one or two hydroxyl groups, carboxyl groups or
ester-forming derivative groups derived from these as ester-forming
functional groups are especially desirable. This serves to improve
reactivity during preparation of the polyester resin, and to
provide especially good weather resistance of the resulting
polyester resin and stability and the like of a resin composition
for film formation prepared from the polyester resin.
[0054] Of the reactive phosphorus-containing compounds represented
by General Formula (I), the compounds represented by chemical
formulae (a) to (e) below are examples of ideal compounds.
##STR00004##
[0055] (In the formula, R.sup.14 represents a hydrogen atom or a
C.sub.1-6 linear or branched alkyl group or alicyclic group).
##STR00005##
[0056] (In the formula, R.sup.15 and R.sup.16 may be the same or
different, and each represents a hydrogen atom or a C.sub.1-6
linear or branched alkyl group or alicyclic group).
##STR00006##
[0057] Of the compounds represented by General Formula (II) above,
the compounds represented by chemical formulae (f) and (g) below
are examples of especially desirable compounds.
##STR00007##
[0058] (In the formula, R.sup.17 represents a hydrogen atom or a
C.sub.1-6 linear or branched alkyl group or alicyclic group).
##STR00008##
[0059] (In the formula, R.sup.18 represents a hydrogen atom or a
C.sub.1-6 linear or branched alkyl group or alicyclic group).
[0060] Of the compounds represented by General Formula (III) above,
the compounds represented by chemical formula (h) below are
examples of especially desirable compounds.
##STR00009##
[0061] (In the formula, R.sup.19 represents a hydrogen atom or a
C.sub.1-6 linear or branched alkyl group or alicyclic group).
[0062] When manufacturing the polyester resin, this reactive
phosphorus-containing compound is preferably dissolved or dispersed
in a univalent alcohol such as methanol or ethanol or a bivalent
alcohol such as ethylene glycol, propylene glycol or butylene
glycol before being added to the reaction system.
[0063] The content of phosphorus atoms derived from the reactive
phosphorus-containing compound in the aqueous polyester resin is
preferably adjusted to a weight ratio of 300 ppm or more relative
to the total of the aqueous polyester resin, and a content of 500
ppm or more is more preferable. The amount of the reactive
phosphorus-containing compound used is preferably adjusted so that
the content of the phosphorus atoms in the aqueous polyester resin
is within the aforementioned range. This serves to impart
particularly good flame retardancy to the aqueous polyester resin.
There is no particular upper limit to how much of this reactive
phosphorus-containing compound is used, but the amount is
preferably adjusted so that the content of phosphorus atoms is
100,000 ppm or less. This serves to prevent polymerization defects
and the like, and prevent a loss of resin properties of the aqueous
polyester resin.
[0064] The amounts of the raw materials used in manufacturing the
polyester resin are preferably adjusted so that the molar ratio of
the total of the carboxyl groups and ester-forming derivative
groups thereof in the raw materials relative to the total of the
hydroxyl groups and ester-forming derivative groups thereof is in
the range of 1:1 to 1:2.5.
[0065] It is also desirable to use suitable amount of a known
polyfunctional compound such as pentaerythritol, trimethylol
propane, dimethylol butanoic acid or a trifunctional carboxylic
acid in order to adjust the molecular weight when preparing the
polyester resin. In particular, when the number of functional
groups (ester-forming function groups) in the reactive
phosphorus-containing compound is one, it is desirable to include
this polyfunctional compound as needed because there is a risk that
the reactive phosphorus-containing compound will act as a
terminating agent.
[0066] In addition, p-hydroxybenzoic acid, univalent aliphatic
alcohols and the like can also be combined as reaction components
other than the above components.
[0067] The polyester resin can be produced by polymerization or
condensation polymerization of the raw materials by a known
polyester manufacturing method. For example, when the polyvalent
carboxylic acid component is a polyvalent carboxylic acid and the
glycol component is a glycol, a direct esterification reaction can
be employed in which the polyvalent carboxylic acid and glycol are
reacted in a single-stage reaction.
[0068] When the polyvalent carboxylic acid component is an
ester-forming derivative of a polyvalent carboxylic acid and the
glycol component is a glycol, on the other hand, the polyester
resin can be manufactured via a first-stage reaction in which the
ester-forming derivative of the polyvalent carboxylic acid is
subjected to an ester exchange reaction with the glycol, and a
second-stage reaction in which the reaction product of the first
reaction is polycondensed. For example, using dimethyl
terephthalate (DMT) as the polyvalent carboxylic acid component and
ethylene glycol (EG) as the glycol component, bishydroxyethylene
terephthalate (BHET) is first produced by an ester exchange
reaction of DMT and EG (first-stage reaction), and this BHET is
then polycondensed (second-stage reaction) to produce polyethylene
terephthalate. In this case, components other than the polyvalent
carboxylic acid component and glycol component are added and
reacted at any timing from the beginning of the first reaction to
the end of the second reaction.
[0069] Methods of manufacturing the polyester resin via the
aforementioned first-stage reaction and second-stage reaction are
here explained in more detail. In the first-stage reaction (ester
exchange reaction), all the raw materials used in manufacturing the
aqueous polyester resin can be included from the beginning in the
reaction system, or else the reactive phosphorus-containing
compound and the like may be added to the reaction system during
the ester polycondensation reaction. When they are loaded all at
once, the ester exchange reaction is accomplished for example by
gradually heating from 150.degree. C. to 260.degree. C. under
normal pressure in a nitrogen gas or other inactive gas atmosphere
with the polyvalent carboxylic acid diester and glycol compound
held in a reaction container.
[0070] The second-stage reaction (polycondensation reaction) is
accomplished for example at a temperature range of 160.degree. C.
to 280.degree. C. under reduced pressure of 6.7 hPa (5 mmHg) or
less.
[0071] In this first-stage reaction and second-stage reaction, a
conventionally known titanium, antimony, lead, zinc, magnesium,
calcium, manganese or alkali metal compound or the like can be
added as a catalyst to the reaction system at any timing.
[0072] When the polyester resin is to be used in preparing a resin
composition for film formation, the number-average molecular weight
of this polyester resin is preferably in the range of 5,000 to
50,000. A number-average molecular weight or 5,000 or more can give
the polyester resin especially excellent durability and water
resistance, and is also effective for improving hydrolysis
resistance. If this number-average molecular weight is 50,000 or
less, on the other hand, excellent solution stability can be
maintained when the polyester resin is dispersed or dissolved in an
aqueous solvent in the resin composition for film formation.
[0073] Moreover, when the polyester resin is to be used in
preparing a resin composition for film formation, the intrinsic
viscosity of this polyester resin is preferably in the range of
0.05 to 1.0. It is thus possible to impart excellent flame
retardancy, durability and water resistance to the resin
composition for film formation, and to improve the long-term
storage stability of a dispersion or solution. That is, with an
intrinsic viscosity of 0.05 or more it is possible to form an
especially strong film from the resin composition for film
formation, while with an intrinsic viscosity of 1.0 or less it is
possible to obtain a liquid dispersion or solution with especially
good long-term storage stability. Especially desirable effects are
obtained if the intrinsic viscosity is in the range of 0.12 to 0.9.
Moreover, optimal effects are obtained if the intrinsic viscosity
is in the range of 0.2 to 0.9.
[0074] A hybrid-type polyester resin is obtained by preparing a
reaction solution containing such a polyester resin together with
silica particles and an alkoxysilane, and reacting the silica
particles and alkoxysilane in the reaction solution by the sol-gel
method.
[0075] A silica sol dispersed in water, an aqueous solvent, alcohol
or the like can be used for the silica particles.
[0076] The average particle diameter of the silica particles is
preferably 50 nm or less, or more preferably 20 nm or less. This
allows for particular improvements in the flame retardancy of the
hybrid-type polyester resin, while also maintaining the
transparency of the hybrid-type polyester resin. There is no
particular lower limit on the average particle diameter of the
silica particles, but at least 4 nm or at least 5 nm is preferable
from the standpoint of availability. The average particle diameter
is a value measured by laser diffraction scattering using a
particle size analyzer.
[0077] Alkoxysilanes are represented by the formula
R.sub.nSiX.sub.4-n in which each R independently represents an
optionally substituted hydrocarbon group or phenyl group. Examples
of R include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl,
octyl and other alkyl groups; cyclopentyl, cyclohexyl and other
cycloalkyl groups; 2-phenylethyl, 2-phenylpropyl, 3-phenylpropyl
and other aralkyl groups; phenyl, tolyl and other aryl groups;
vinyl, allyl and other alkenyl groups; chloromethyl,
.gamma.-chloropropyl, 3,3,3-trifluoropropyl and other
halogen-substituted hydrocarbon groups; and
.gamma.-methacryloxypropyl, .gamma.-glycidoxypropyl,
3,4-epoxycyclohexylethyl, .gamma.-mercaptopropyl and other
substituted hydrocarbon groups. X represents an alkoxy group.
[0078] Moreover, n in the formula is preferably an integer from 0
to 3 or particularly an integer from 0 to 2, or in other words the
alkoxysilane is a tetrafunctional, trifunctional or bifunctional
alkoxysilane. Examples of tetrafunctional alkoxysilanes include
tetramethoxysilane, tetraethoxysilane and the like. Examples of
trifunctional alkoxysilanes include methyl trimethoxysilane, methyl
triethoxysilane, methyl triisopropoxysilane,
propyltrimethoxysilane, phenyl trimethoxysilane, phenyl
triethoxysilane, 3,3,3-trifluoropropyl trimethoxysilane and the
like. Examples of bifunctional alkoxysilanes include dimethyl
dimethoxysilane, dimethyl diethoxysilane, diphenyl dimethoxysilane,
diphenyl diethoxysilane, methyl phenyl dimethoxysilane and the
like.
[0079] Water or a mixed solvent containing water and another
solvent can be used as the solvent in the reaction solution.
Examples of other solvents include toluene, xylene, hexane, ethyl
heptaneacetate, butyl acetate, methyl ethyl ketone, methyl isobutyl
ketone, methyl ethyl ketoxime and the like.
[0080] The contents of the polyester resin, silica particles and
alkoxysilane in the reaction solution can be set appropriately, but
preferably the content of the polyester resin is in the range of 1
mass % to 50 mass %, the content of the silica particles is in the
range of 1 mass % to 60 mass % of the polyester resin, and the
content of the alkoxysilane is in the range of 0.3 mass % to 20
mass % of the polyester resin. In this way is possible to control
gelling and maintain the stability of the reaction solution, while
the effects of improving the flame retardancy of the hybrid-type
polyester resin and preventing scattering of high-temperature
droplets during combustion are also increased. If the silica or
alkoxysilane content is excessive, the stability of the reaction
solution is reduced and there is a risk of gelling, while if the
alkoxysilane content is too low, there may not be sufficient
improvement in the flame retardancy of the hybrid-type polyester
resin, and if the silica content is too low, a sufficient
high-temperature droplet scattering prevention effect may not be
achieved.
[0081] A catalyst is preferably compounded in the reaction
solution. This catalyst may be an acid catalyst or a basic
catalyst. Examples of acid catalysts include organic acids such as
acetic acid, chloroacetic acid, citric acid, benzoic acid,
dimethylmalonic acid, formic acid, propionic acid, glutaric acid,
glycolic acid, maleic acid, malonic acid, toluenesulfonic acid and
oxalic acid; inorganic acids such as hydrochloric acid, nitric
acid, halogenated silane and the like; and acidic sol fillers such
as acidic colloidal silica and acidic titania sol and the like.
Examples of basic catalysts include aqueous solutions of sodium
hydroxide, calcium hydroxide and other hydroxides of alkali metals
or alkali earth metals; and ammonia water, aqueous amine solutions
and the like. One of these catalysts may be used alone, or two or
more kinds may be used together.
[0082] A phosphorus flame retardant may also be included in the
reaction solution. In this case, the flame retardancy of the
hybrid-type polyester resin can be improved because the phosphorus
flame retardant is mixed into the hybrid-type polyester resin.
[0083] Examples of the phosphorus flame retardant include butyl
bis(3-hydroxypropyl)phosphine oxide, ammonium polyphosphate and
other polyphosphate salts, and guanidine phosphate derivatives and
the like.
[0084] It is desirable to use the reactive phosphorus-containing
compound described above as the phosphorus flame retardant. This
serves to further improve the flame retardancy of the hybrid-type
polyester resin.
[0085] When such a phosphorus flame retardant is used, it is
preferably used in the amount of 1 mass % to 40 mass % of the
polyester resin.
[0086] Promoting a sol-gel reaction of the alkoxysilane and silica
particles in the reaction solution serves to hybridize the siloxane
produced by the reaction with the polyester resin. The sol-gel
reaction may be performed at room temperature, or with heating of
the reaction solution. For example, the sol-gel reaction may be
performed with the temperature of the reaction solution at
10.degree. C. to 90.degree. C., or preferably 20.degree. C. to
80.degree. C., or more preferably 30.degree. C. to 60.degree. C.
The reaction time depends partly on the reaction temperature, but
may be in the range of 1 hour to 48 hours for example.
[0087] The hybrid-type polyester resin produced by thus hybridizing
the polyester resin and siloxane acquires excellent flame
retardancy and also the property of being less likely to scatter
high-temperature droplets even when it burns, while maintaining the
excellent properties inherent in polyester resin. Furthermore, the
flame retardancy of the hybrid-type polyester resin can be further
improved by using a phosphorus-containing polyester resin, or
including a phosphorus flame retardant in the reaction solution. In
addition, excellent water dispersibility or water solubility can be
imparted to the hybrid-type polyester resin by using a hydrophilic
component as a raw material of the polyester.
[0088] This hybrid-type polyester resin can be used for various
applications. In particular, as discussed above, because of its
excellent durability and the like this hybrid-type polyester resin
can be used favorably in preparing a resin composition for film
formation.
[0089] When the hybrid-type polyester resin has been given
excellent water dispersibility or solubility, the resin composition
for film formation can be applied as a water-based composition, and
excellent worker safety and environmental protection are obtained
when a base material is processed using this resin composition for
film formation. Penetrating agents, flame retardants, anti-static
agents, pigments, dyes, antioxidants, UV absorbents, antifoaming
agents, dispersion aids and other additives can also be included as
necessary in this resin composition for film formation.
[0090] When the resin composition for film formation is used to
treat textile products, examples of treatment methods include
methods in which the resin composition for film formation is
applied to a woven, knitted or nonwoven textile or carpet, web or
the like by immersion, padding, coating or the like, methods in
which the resin composition for film formation is applied to the
threads with a sizing machine as in a sizing method, and methods in
which such treated threads are then woven and the like.
[0091] When the resin composition for film formation is used to
surface-treat a polyester film of a PET film, the method of use may
be a method in which the resin composition for film formation is
applied for example to the manufactured PET film ex post. In other
methods, the resin composition for film formation is applied to the
surface of the polyester film at any stage in the process of
forming a PET or other polyester film by ordinary methods. In the
latter case, PET film formation may involve various steps including
drying, melt extrusion, unstretched film formation, biaxial
stretching and heat treatment for example, and the resin
composition for film formation can be applied to the film by
dipping, curtain coating, gravure coating, wire bar methods, spray
coating, reverse coating, die coating or the like during any of
these steps.
[0092] In addition to the applications given above, a resin
composition for film formation containing the hybrid-type polyester
resin may be applied, for example, as a coating agent for metal,
glass, paper, wood and the like, as an overcoat agent for
electronic substrates and the like, as an anchor coat agent, ink
binder or other adhesive agent, and as a surface treatment agent
for polyvinyl chloride, polycarbonate and other plastic films and
the like.
[0093] A polyester film, textile or the like that is
surface-treated with the resin composition for film formation
thereby acquires superior flame retardancy, and the hybrid-type
polyester resin on the surface does not break down easily or
scatter high-temperature droplets even if it is burned during a
fire or the like. Thus, the spread of damage can be controlled
during a fire or the like.
EXAMPLES
[0094] The present invention is explained in more detail below
using example. The "parts" and "%" values used below are all based
on mass unless otherwise specified.
Synthesis Example 1
[0095] 135.9 parts of dimethylterephthalic acid, 35.0 parts of
dimethylisophthalic acid, 35.5 parts of sodium 5-sulfonate
dimethylisophthalic acid, 124.2 parts of ethylene glycol and 0.1
part of titanium potassium oxalate as a catalyst were added to a
reaction container to prepare a reaction solution, which was then
heated to 200.degree. C. with agitation at normal pressure in a
nitrogen atmosphere. Next, the reaction temperature was gradually
raised to 260.degree. C. over the course of 4 hours to terminate
the ester exchange reaction. This was then gradually depressurized
at 260.degree. C., and a polycondensation reaction was performed
for 2 hours under conditions of 260.degree. C., 0.67 hPa (0.5 mmHg)
to produce an aqueous polyester resin with an intrinsic viscosity
of 0.60 and a number-average molecular weight of 27,000.
[0096] 25 parts of this polyester resin and 75 parts of water were
added to a dissolving bath, and dissolved with agitation for 2
hours at a temperature of 80.degree. C. to 95.degree. C. to obtain
25% aqueous solution A of polyester resin.
Synthesis Example 2
[0097] In Synthesis Example 1, the amount of the
dimethylisophthalic acid used was changed to 44.7 parts, the amount
of the sodium 5-sulfonate dimethylisophthalic acid used was changed
to 29.6 parts, and the amount of the ethylene glycol used was
changed to 116.8 parts in the preparation of the reaction solution.
In addition, 12.7 parts of diethylene glycol were further added to
the reaction solution. An aqueous polyester resin with an intrinsic
viscosity of 0.57 and a number-average molecular weight of 25,000
was obtained under the same conditions as in Synthesis Example 1
with these exceptions.
[0098] 25 parts of this polyester resin, 70 parts of water and 5
parts of ethylene glycol mono-t-butyl ether were added to a
dissolving bath, and dissolved with agitation for 2 hours at a
temperature of 80.degree. C. to 95.degree. C. to obtain 25% aqueous
solution B of polyester resin.
Synthesis Example 3
[0099] In Synthesis Example 1, the amount of the
dimethylterephthalic acid used was changed to 48.6 parts, the
amount of the dimethylisophthalic acid used was changed to 46.6
parts, the amount of the sodium 5-sulfonate dimethylisophthalic
acid used was changed to 17.8 parts, and the amount of the ethylene
glycol used was changed to 195.3 parts in the preparation of the
reaction solution. In addition, 12.7 parts of diethylene glycol,
115.5 parts of the reactive phosphorus-containing compound
represented by chemical formula (e) above and 2.7 parts of
trimethylol propane were further added to the reaction solution. An
aqueous polyester resin with an intrinsic viscosity of 0.50 and a
number-average molecular weight of 12,000 was obtained under the
same conditions as in Synthesis Example 1 with these
exceptions.
[0100] 25 parts of this polyester resin, 70 parts of water and 10
parts of ethylene glycol mono-t-butyl ether were added to a
dissolving bath, and dissolved with agitation for 2 hours at a
temperature of 80.degree. C. to 95.degree. C. to obtain 25% aqueous
solution C of polyester resin.
Example 1
[0101] 100 parts of the polyester aqueous solution A obtained in
Synthesis Example 1 above, 50 parts of water, 50 parts of methanol,
10 parts of colloidal silica (30% aqueous solution), 5 parts of
ammonium polyphosphate, 0.1 parts of tetraethoxysilane and 0.3
parts of 25% ammonia water were placed in a reaction container, and
reacted for 5 hours at 25.degree. C., 500 rpm. The methanol and the
alcohol produced by the reaction were then distilled off under
reduced pressure to obtain an aqueous solution of a hybrid-type
polyester resin.
Example 2
[0102] In Example 1, the amount of tetraethoxysilane used was
changed to 1 part. An aqueous solution of a hybrid-type polyester
resin was obtained under the same conditions as in Example 1 with
this exception.
Example 3
[0103] In Example 1, the amount of tetraethoxysilane used was
changed to 5 parts. An aqueous solution of a hybrid-type polyester
resin was obtained under the same conditions as in Example 1 with
this exception.
Example 4
[0104] In Example 1, the polyester aqueous solution B synthesized
in Synthesis Example 2 above was used instead of polyester aqueous
solution A, IPA silica sol (solids content 30%) was used instead of
colloidal silica (30% aqueous solution), the amount of ammonium
polyphosphate used was changed to 10 parts, and the amount of
tetraethoxysilane used was changed to 0.5 parts. An aqueous
solution of a hybrid-type polyester resin was obtained under the
same conditions as in Example 1 with these exceptions.
Example 5
[0105] In Example 4, propyl trimethoxysilane was used instead of
tetraethoxysilane, and the amount of ammonium polyphosphate used
was changed to 5 parts. An aqueous solution of a hybrid-type
polyester resin was obtained under the same conditions as in
Example 4 with these exceptions.
Example 6
[0106] In Example 4, dimethyl diethoxysilane was used instead of
tetraethoxysilane, and the amount of ammonium polyphosphate used
was changed to 1 part. An aqueous solution of a hybrid-type
polyester resin was obtained under the same conditions as in
Example 4 with these exceptions.
Example 7
[0107] In Example 4, butyl bis(3-hydroxypropyl)phosphine oxide was
used instead of ammonium polyphosphate. An aqueous solution of a
hybrid-type polyester resin was obtained under the same conditions
as in Example 4 with this exception.
Example 8
[0108] In Example 5, butyl bis(3-hydroxypropyl)phosphine oxide was
used instead of ammonium polyphosphate. An aqueous solution of a
hybrid-type polyester resin was obtained under the same conditions
as in Example 5 with this exception.
Example 9
[0109] In Example 6, butyl bis(3-hydroxypropyl)phosphine oxide was
used instead of ammonium polyphosphate. An aqueous solution of a
hybrid-type polyester resin was obtained under the same conditions
as in Example 6 with this exception.
Example 10
[0110] In Example 7, the amount of IPA silica gel used was changed
to 1 part, and the amount of butyl bis(3-hydroxypropyl)phosphine
oxide used was changed to 5 parts. An aqueous solution of a
hybrid-type polyester resin was obtained under the same conditions
as in Example 7 with these exceptions.
Example 11
[0111] In Example 10, the amount of IPA silica gel used was changed
to 50 parts. An aqueous solution of a hybrid-type polyester resin
was obtained under the same conditions as in Example 10 with this
exception.
Example 12
[0112] In Example 10, HCA-HQ (the reactive phosphorus-containing
compound (d) represented by chemical formula (d) above) was used
instead of butyl bis(3-hydroxypropyl)phosphine oxide, and the
amount of IPA silica sol used was changed to 10 parts. An aqueous
solution of a hybrid-type polyester resin was obtained under the
same conditions as in Example 10 with these exceptions.
Example 13
[0113] In Example 4, 1M HCl aqueous solution was used instead of
25% ammonia water. An aqueous solution of a hybrid-type polyester
resin was obtained under the same conditions as in Example 4 with
this exception.
Example 14
[0114] In Example 5, 1M HCl aqueous solution was used instead of
25% ammonia water. An aqueous solution of a hybrid-type polyester
resin was obtained under the same conditions as in Example 5 with
this exception.
Example 15
[0115] In Example 6, 1M HCl aqueous solution was used instead of
25% ammonia water. An aqueous solution of a hybrid-type polyester
resin was obtained under the same conditions as in Example 6 with
this exception.
Example 16
[0116] In Example 7, the polyester aqueous solution C synthesized
in Synthesis Example 3 above was used instead of polyester aqueous
solution B, methanol silica sol (solids content 30%) was used
instead of IPA silica sol, and the amount of butyl
bis(3-hydroxypropyl)phosphine oxide used was changed to 5 parts. An
aqueous solution of a hybrid-type polyester resin was obtained
under the same conditions as in Example 7 with these
exceptions.
Example 17
[0117] In Example 16, propyl trimethoxysilane was used instead of
tetraethoxysilane. An aqueous solution of a hybrid-type polyester
resin was obtained under the same conditions as in Example 16 with
this exception.
Example 18
[0118] In Example 16, dimethyl diethoxysilane was used instead of
tetraethoxysilane. An aqueous solution of a hybrid-type polyester
resin was obtained under the same conditions as in Example 16 with
this exception.
Example 19
[0119] In Example 16, no butyl bis(3-hydroxypropyl)phosphine oxide
was used. An aqueous solution of a hybrid-type polyester resin was
obtained under the same conditions as in Example 16 with this
exception.
Example 20
[0120] In Example 17, no butyl bis(3-hydroxypropyl)phosphine oxide
was used. An aqueous solution of a hybrid-type polyester resin was
obtained under the same conditions as in Example 17 with this
exception.
Example 21
[0121] In Example 18, no butyl bis(3-hydroxypropyl)phosphine oxide
was used. An aqueous solution of a hybrid-type polyester resin was
obtained under the same conditions as in Example 18 with this
exception.
Comparative Example 1
[0122] The polyester aqueous solution A synthesized in Synthesis
Example 1 above was used as is.
Comparative Example 2
[0123] The polyester aqueous solution B synthesized in Synthesis
Example 2 above was used as is.
Comparative Example 3
[0124] The polyester aqueous solution C synthesized in Synthesis
Example 3 above was used as is.
Comparative Example 4
[0125] In Example 7, no tetraethoxysilane was used. An aqueous
solution of a polyester resin was obtained under the same
conditions as in Example 4 with this exception.
Comparative Example 5
[0126] In Example 7, no IPA silica sol was used. An aqueous
solution of a polyester resin was obtained under the same
conditions as in Example 4 with this exception.
Comparative Example 6
[0127] In Example 7, no tetraethoxysilane and butyl
bis(3-hydroxypropyl)phosphine oxide were used. An aqueous solution
of a polyester resin was obtained under the same conditions as in
Example 4 with this exception.
Comparative Example 7
[0128] In Example 7, no tetraethoxysilane and IPA silica sol were
used. An aqueous solution of a polyester resin was obtained under
the same conditions as in Example 4 with this exception.
[0129] [Combustion Test]
[0130] Polyester tropical fabric was treated by the padding method
using the hybrid-type polyester resin aqueous solutions obtained in
the examples and the polyester resin aqueous solutions obtained in
the comparative examples, dried for 5 minutes at 110.degree. C.,
and cured for 1 minute at 180.degree. C. to obtain test fabric.
[0131] This test fabric was subjected to combustion testing
according to the 45.degree. microburner method (JIS L 1091 A-1) and
the contact flame method (JIS L 1091 D).
[0132] The results are shown in Table 1. According to these
results, good evaluations were obtained for Examples 1 to 21 by
both the A-1 method and the D method, and even when combustion
occurred there was no dripping of high-temperature droplets.
TABLE-US-00001 TABLE 1 Examples 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15
Raw Polyester resin 25% 100 100 100 material aqueous solution A
compo- Polyester resin 25% 100 100 100 100 100 100 100 100 100 100
100 100 sition aqueous solution E (parts) Polyester resin 25%
aqueous solution C Water 50 50 50 50 50 50 50 50 50 50 50 50 50 50
50 Methanol 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 Colloidal
silica (30%) 10 10 10 Methanol silica sol (30%) IPA silica sol
(30%) 10 10 10 10 10 10 1 50 10 10 10 10 Butyl bis(3- 10 5 1 5 5
hydroxypropyl)phosphine oxide Ammonium polyphosphate 5 5 5 10 5 1
10 5 1 HCA-HQ 5 Dimethyl diethoxysilane 0.5 0.5 0.5 Propyl
trimethoxysilane 0.5 0.5 0.5 Tetraethoxysilane 0.1 1 5 0.5 0.5 0.5
0.5 0.5 0.5 25% ammonia water 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3
0.3 0.3 0.3 1M HCl aqueous solution 0.3 0.3 0.3 Evalu- A-1
Fractions 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 ation method Dripping of N
N N N N N N N N N N N N N N droplets? D No. of Vertical 5 5 5 6 5 4
6 5 4 4 6 5 6 5 4 method flame Horizontal 5 5 5 6 5 4 6 5 4 4 6 5 6
5 4 contacts Dripping of N N N N N N N N N N N N N N N droplets?
Examples Comp. Examples 16 17 18 19 20 21 1 2 3 4 5 6 7 Raw
Polyester resin 25% 100 material aqueous solution A compo-
Polyester resin 25% 100 100 100 100 100 sition aqueous solution E
(parts) Polyester resin 25% 100 100 100 100 100 100 100 aqueous
solution C Water 50 50 50 50 50 50 50 50 50 50 Methanol 50 50 50 50
50 50 50 50 50 50 Colloidal silica (30%) Methanol silica sol (30%)
10 10 10 10 10 10 IPA silica sol (30%) 10 10 Butyl bis(3- 5 5 5 10
10 10 hydroxypropyl)phosphine oxide Ammonium polyphosphate HCA-HQ
Dimethyl diethoxysilane 0.5 0.5 Propyl trimethoxysilane 0.5 0.5
Tetraethoxysilane 0.5 0.5 0.5 25% ammonia water 0.3 0.3 0.3 0.3 0.3
0.3 0.3 0.3 0.3 0.3 1M HCl aqueous solution Evalu- A-1 Fractions 3
3 3 3 3 3 1 1 3 1 3 1 3 ation method Dripping of N N N N N N Y Y Y
N Y N Y droplets? D No. of Vertical 6 6 6 5 5 5 1 1 4 5 4 3 4
method flame Horizontal 6 6 6 5 5 5 1 1 4 5 4 3 4 contacts Dripping
of N N N N N N Y Y Y N Y N Y droplets?
* * * * *